Nickel-catalyzed copolymerization of ethylene

ABSTRACT

Preparation of ethylene copolymers from ethylene and polar and/or non-polar comonomers in the presence of selected nickel-containing catalysts.

This is a division of application Ser. No. 091,951 filed Sept. 1, 1987and now U.S. Pat. No. 4,906,754, which is a divisional application ofSer. No. 787,148, filed Oct. 15, 1985, and now U.S. Pat. No. 4,698,403.

BACKGROUND OF THE INVENTION

1. Technical Field

This invention relates to the preparation of ethylene/1-olefincopolymers in the presence of selected nickel-containing catalysts.

2. Background

Various nickel-containing compounds, usually in complexed form, areknown in the art as catalysts for polymerizing ethylene to linear1-olefin oligomers. Certain of these catalysts, under selectedconditions, are reported to polymerize ethylene to high molecular weightpolyethylene. The copolymerization of ethylene with polar or non-polar1-olefins, catalyzed by nickel-containing compounds, is unknown in theart.

Also well known in the art are copolymers of ethylene and non-polar orpolar 1-olefin comonomers, prepared with nickel-free catalysts, such asthe organometallic Ziegler-Natta coordination-type catalysts andfree-radical catalysts. The most commonly used polar 1-olefins are ofthe formula CH₂ ═C(R)X wherein R is H or CH₃ and X is a polar group,such as OC(0)CH₃, OR' or CO₂ R, wherein R' is alkyl, cylcoalkyl, aryl orhalogen. Copolymers of ethylene and 1-olefinic comonomers containingpolar functions attached other than to the vinyl group are also known,such comonomers being of the formula CH₂ ═CH(CH₂)_(n) X wherein X is apolar group and n is an integer and is at least one, or of the formulaCH₂ ═CHX(Z)_(n) wherein X is a hydrocarbon group having at least onecarbon atom, Z is a polar group and n is at least one.

The difficulty of copolymerizing polar 1-olefin comonomers with ethyleneusing coordination-type catalysts, as compared to non-polar 1-olefins,is known to be greatest when the polar group is close to the vinylgroup; it is also known to become easier the more closely the polarcomonomer resembles a non-polar comonomer. Rules for achieving thissimilarity by various types of shielding are known in the art.

It has been discovered that certain, selected nickel-based catalystswhich are known for use in the preparation of ethylene oligomers and, insome cases, polyethylene, are useful for preparing ethylene/1-olefincopolymers, including those containing polar substituents. Alsodiscovered and disclosed herein are novel nickel-containing catalystswhich are similarly useful.

SUMMARY OF THE INVENTION

This invention provides: (1) a process for copolymerizing ethylene with1-olefins in the presence of selected nickel-containing catalysts, (2)novel nickel-containing catalyst compositions and (3) processes forcatalyst preparation.

The invention herein resides in the copolymerization process comprisingcontacting and reacting ethylene, in an oxygen-free atmosphere, at atemperature in the range of about 0° C. to about 200° C., in thepresence of a selected nickel-containing catalyst, with one or more1-olefins of the formula CH₂ ═CHX wherein:

X is --R, --OR, --R_(H) R_(F), --OR_(F) --Si(OR¹)_(3-x) R¹)_(x),--OSi(OR¹)_(3-x) R¹)_(x), --N(R')(R²), --Sn(R¹)₃ and --B(R¹)₂ ;

R is hydrocarbyl,provided, however: (i) conjugated aliphaticunsaturation and terminal --C.tbd.CH groups are excluded, and anyunsaturation is separated from the enyl group CH₂ ═CH-- by at least onecarbon atom; and (ii) any functional substituent selected from --OH,--CO₂ R², --CO₂ Si(OR¹)_(3-x) (R¹)_(x), --C(O)N(R¹)₂, --N(CH₃)₂, --SOR²,--SO₂ R² or --OSO₂ R² is separated from the enyl group CH₂ ═CH by atleast two carbon atoms;

R_(H) is C₁₋₂₀ hydrocarbylene;

R_(F) is C₁₋₂₀ perfluorocarbyl, optionally containing in-chain etheroxygen;

R' is C₂₋₁₀ hydrocarbyl;

x is 0 or an integer of 1 to 3;

each R¹, independently, is

H or C₁₋₂₀ hydrocarbyl; and

R² is C₁₋₂₀ hydrocarbyl.

The nickel-containing catalysts used in the process of this inventionconsist essentially of one or more of the following:

1(a) The dinickel compound of the formula ##STR1## wherein:

R³ and each R⁴, independently, is

H or C₁₋₂₀ hydrocarbyl;

X¹ is O or S;

E¹ is P, As or Sb; and

each of R⁵ and R⁶, independently, is H, C₁₋₂₀ hydrocarbyl or afunctional group selected from --OR², --Cl, --CO₂ R², --CO₂ M,--C(O)N(R¹)₂, --C(O)R², --SR², --SO₂ R², --SOR², --OSO₂ R²,--P(O)(OR²)_(2-y) (R¹)_(y), --CN, --NHR², --N(R²)₂, ##STR2##--Si(OR¹)_(3-x) (R¹)_(x), --OSi(OR¹)_(3-x) (R¹)_(x), --NO₂, --SO₃ M,--PO₃ M₂ and --P(O)(OR²)₂ M wherein M is alkali or alkaline earth metal,ammonium, quaternary ammonium, phosphonium or arsonium, y is 0, 1 or 2and R¹, each R², independently, and x are as defined above, or R⁵ andR⁶, taken together, is a substituted or unsubstituted C₅₋₈ alicyclic,C₅₋₈ heterocyclic or C₆₋₁₄ aromatic ring, the heteroatom of theheterocyclic ring being selected from O, N and S;

1(b) the nickel compound of the formula ##STR3## wherein:

R³, R⁴, R⁵, R⁶, X¹ and E¹ are defined as above and L¹ is a weaklycoordinating ligand, or R³ and L¹ taken together is ##STR4##

wherein R" is H, C₁₋₂₀ hydrocarbyl or oxyhydrocarbyl or N(R²)₂ whereineach R², independently, is C₁₋₂₀ hydrocarbyl;

1(c) the nickel-containing compound of the formula ##STR5## wherein:

R¹, R⁴, R⁵, R⁶, X¹ and E¹ are defined as above;

each R⁷, independently, is H, --OSi(R"')₃, C₁₋₂₀ alkyl or oxyalkyl,C₆₋₂₀ aryl, alkaryl, aralkyl or oxyaryl, N(R²)₂ wherein R² is as definedabove, or halogen, or both R⁷ groups, taken together, is a 5 to8-membered heterocyclic ring wherein the heteroatom is selected from O,N and S; and

each R"', independently, is C₁₋₂₀ alkyl or oxyalkyl, C₆₋₂₀ aryl,alkaryl, aralkyl or oxyaryl;

(2) the mixture comprising:

(i) the nickel compound of the formula ##STR6## wherein: R³, R⁴, R⁵, R⁶,X¹ and E¹ are defined as above and L² is a strongly coordinating ligand;and

(ii) an acceptor compound which can react irreversibly with L² ;

(3) the mixture comprising:

(i) the nickel compound of the formula ##STR7## R⁴, R⁵, R⁶, X¹ and E¹are defined as above; and (ii) a suitable alkylating or arylatingcompound; and

(4) the mixture as described in U.S. Pat. No. 3,686,159 and comprising:

(i) one or more zero-valent olefin-nickel compounds or x-allyl nickelcompounds, or a nickel(I) or nickel(II) compound capable of forming saidcompounds in the presence of a reducing agent; and

(ii) the phosphorane of the formula

    (R.sup.4).sub.3 P═C(R.sup.5)--C(O)R.sup.6

wherein

R⁴, R⁵ and R⁶ are defined as above, with the proviso that at least oneR⁴ is aryl or substituted

Preferably, the nickel compound (4)(i) isbis(1,5-cyclooctadiene)nickel(0).

DETAILED DESCRIPTION OF THE INVENTION

By "functional substituents" is meant polar radicals which areunreactive under polymerizing conditions. Functional substituentsinclude but are not limited to --OH, OR², --Cl, --CO₂ R², --CO₂ M,--C(O)N(R¹)₂, --C(O)R², --SR², --SO₂ R², --SO₂ R², --OSO₂ R²,--P(O)(OR²)_(2-y) (R¹)_(y), --CN, --NHR², --N(R²)₂, ##STR8## --CF₃,--Si(OR¹)_(3-x) (R¹)_(x), --OSi(OR¹)_(3-x) (R¹)_(x), --NO₂, --SO₃ M,--PO₃ M₂, --P(O)(OR²)₂ M, --CO₂ Si(OR¹)_(3-x) (R¹)_(x) and --P(R¹)₂Cr(CO)₅ wherein M is alkali metal, ammonium or quaternary ammonium andR¹, R², x and y are as defined above.

The term "in-chain" (heteroatom) is intended to include both the main(backbone) chain and any side chain. Preferred in-chain heteroatoms are--0--, ##STR9## and --S--.

By hydrocarbyl is meant an aliphatic, alicyclic, aromatic or mixedaliphatic-aromatic monovalent radical, optionally containing one or morefunctional substituents and/or one or more in-chain heteroatoms whichare inert under polymerizing conditions.

By hydrocarbylene is meant a divalent radical which is otherwise definedas for hydrocarbyl.

By weakly coordinating ligand (L¹) is meant a compound which can bond tonickel, but is readily displaced therefrom by the olefin which is beingpolymerized. Weakly coordinating ligands (L¹) include but are notlimited to pyridine, piperidine, alkyl ethers, tetrahydrofuran, alkyland aryl nitriles and dinitriles, alcohols, amides, aliphatic esters andtertiary amines.

By strongly coordinating ligand (L²) is meant a compound which can bondto nickel sufficiently strongly to displace therefrom part or all of theolefin which is being polymerized. Strongly coordinating ligands (L²)include but are not limited to compounds of the formula E¹ (R¹)₃ whereinE¹ and R¹ are defined as above.

By acceptor compound is meant a compound which bonds to (complexes) aligand more strongly than does nickel. Acceptor compounds include butare not limited to organic oxidants, such as amine oxides, peroxides andhydroperoxides, alkylating compounds and Group VIII metal complexes.Specific examples are trimethylamine oxide, di-t-butylperoxide,cyclohexylhydroperoxide, methyl iodide, trimethylsilyl iodide,bis(benzonitrile)palladium dichloride, bis(1,5-cyclooctadiene)nickel(0),nickel tetracarbonyl, 2,4-pentanedionatobis-(ethylene)rhodium(I) andethylene pentacarbonylchromium(0).

By alkylating or arylating compound is meant a compound which is capableof chemically transferring alkyl or aryl groups, as the case may be, tonickel. Alkylating and arylating compounds include but are not limitedto alkyl and aryl iodides, aluminum alkyls and aryls, transition metalalkyl- and aryl-containing compounds, such asdimethyl(1,5-cyclooctadiene)platinum(II) anddimethylbis(phosphine)nickel, and other conventional reagents capable oftransferring alkyl and/or aryl radicals.

In catalyst mixture (2), the acceptor compound (2)(ii) is present in theamount of about 0.1 to >1 mole, preferably about 0.5 to about 2 moles,per mole of nickel compound (2)(i).

In catalyst mixture (3), the alkylating or arylating compound (3)(ii) ispresent in the amount of about 0.01 to about 2 moles, preferably about0.1 to about 1.5 moles, per mole of nickel compound 3(i).

In catalyst mixture (4), the molar ratio of the nickel compound to thephosphorane can vary from about 1:1 to about 1:10, preferably about 1:1to about 1:3.

The catalyst components (i) and (ii) in mixtures (2), (3) and (4) can beintroduced to the polymerization reactor together or separately assolids or in solution and/or together with the comonomer and/or thesolvent. The presence of comonomer during addition of the catalystcomponents in (4) may stabilize the nickel(0) species or its precursorby directly complexing to the nickel.

Catalyst 1(a) is produced when mixture (2) is subjected to polymerizingconditions in the absence of ethylene and/or comonomer. Morespecifically, catalyst 1(a) can be prepared by heating mixture (2) in asolvent at a temperature of about 0° C. to about 150° C., preferablyabout 20° C. to about 60° C., and at any suitable pressure, preferablyatmospheric pressure, for about 1 minute to about 48 h. Preferredsolvents are aromatic solvents, such as benzene, toluene and xylene. Thereaction mixture can be cooled to below room temperature to facilitateprecipitation or crystallization of the catalyst 1(a).

Catalyst 1(b) is prepared by contacting and reacting catalyst mixture(4) with an excess of the weakly coordinating ligand L¹, defined asabove. L¹ may also serve as a solvent for the reaction. Specifically,mixture (4) and ligand L¹ are mixed in the molar proportion of ≧1 moleof L¹ per mole of catalyst component 4(i), preferably about 10 to about1000 moles of L¹ per mole of 4(i), in a suitable solvent, and reacted ata temperature of about 0° C. to about 150° C. preferably at about 20° C.to about 60° C., for about one minute to about 72 h, at any suitablepressure, preferably atmospheric pressure. The catalyst 1(b) is isolatedby conventional techniques, such as by filtration or, if dissolved, byprecipitation with a non-solvent or by solvent evaporation. Suitablesolvents include aromatic compounds, such as benzene or toluene;alcohols, such as ethanol or isopropanol; ethers, such astetrahydrofuran or diethylether; nitriles, such as acetonitrile orbenzonitrile; ketones, such as acetone or methylphenylketone; amides,such as acetamide or dimethylformamide; esters, such as ethyl acetate ormethyl benzoate; and dimethylsulfoxide. Aromatic hydrocarbons, such astoluene or benzene, are preferred. Halogen-containing solvents, such aschloroform, methyl iodide or bromobenzene, should be avoided because ofpossible reaction with the nickel-containing compounds.

It will be understood that catalyst 1(b) is similar in structure tocatalyst component 2(i) except that the strongly coordinating ligand L²is replaced with the weakly coordinating ligand L¹.

Catalyst 1(c) is prepared by heating the catalyst mixture (3), whereinthe alkylating or arylating agent 3(ii) is an aluminum compound, in asuitable solvent, such as benzene or toluene, at a temperature of about-25° C. to about 120° C., preferably at about 0° C. to about 60° C., forabout 1 minute to about 60 minutes. Catalyst 1(c) can be isolated asdescribed above for catalyst 1(b).

The nickel-containing catalyst component 2(i) is a known compound; itspreparation is described in U.S. Pat. Pat. 4,293,502.

The nickel containin9 catalyst component 3(i) wherein X¹ is O can beprepared:

(a) by the procedure descibed by Moulton and Shaw in J. Chem. Soc.Dalton, 300 (1980);

(b) by reacting the corresponding ylid, bis(1,5-cyclooctadiene)nickel,with an approximately 10 to 100 molar excess of methyl methacrylate inan aromatic solvent, such as toluene or benzene, at a temperature ofabout 20° C. to about 100° C.;

(c) by reacting either catalyst 1(a), catalyst component 2(i) orcatalyst 1(b) with a β-ketophosphine of the formula (R⁴)₂ PCH(R⁵)C(O)R⁶,wherein R⁴, R⁵ and R⁶ are defined as above, in an aromatic solvent, suchas toluene or benzene, at a temperature of about 20° C. to about 120°C., for about 1 are mixed in the molar are mixed in the molar minute toabout 48 h;

(d) by reacting, in the presence of a strong alkali, such as sodiumhydroxide or potassium ethoxide, in a suitable solvent, such as toluene,benzene, tetrahydrofuran (THF) or ether, at a temperature in the rangeof about -10° C. to about 100° C., the aforesaid β-ketophosphine and thenickel compound of the formula (R⁸)₂ Ni(L³)₂ or (X²)_(p) Ni(L³)_(m)wherein:

each R⁸, independently, is C₁₋₂₀ alkyl or alkoxy or C₆₋₂₀ aryl oraryloxy, preferably methyl, methoxy, phenyl or phenoxy;

each L³, independently, is a monodentate ligand, such as E¹ (R¹) whereinR¹ and E¹ are defined as above, or two L³ groups taken together are abidentate ligand, such as 1,10-phenanthroline, bipyridine or1,2-bis(dimethylphosphino)ethane or its diphenyl analog;

each X², independently, is a functional group, such as halogen, CN orSO₄ ;

p is 1 or 2; and

m is 0, 1 or 2; or

(e) by subjecting any of the catalysts 1(a)-(c), or the catalystemployed by Keim et al., Angew. Chem Int. Ed. Engl., 17, No. 6, 466(1978), to ethylene oligomerization or polymerization conditions asdescribed, for example, by Keim et al. in the aforesaid publication.After removing the oligomer by distillation, or the polymer byfiltration, the crystalline orange catalyst component 3(i) is recoveredby partial evaporation of the solvent at or below atmospheric pressureat a temperature of about 20° C. to about 100° C.

The nickel-containing catalyst component 3(i) wherein X¹ is S can beprepared by reacting the compound 3(i) wherein X is O with a molarexcess of H₂ S in an alkanol, such as methanol or ethanol, at atemperature in the range of about -10° C. to about 100° C., preferablyabout 10° C. to about 40° C., at a pressure of at least one atmosphere;excess H₂ S and the alkanol are removed under reduced pressure and thecatalyst component can be purified by recrystallization from analkanol-dichloromethane mixture

Alternatively, the nickel-containing catalyst component 3(i) can beprepared from a 3-thioketophosphine of the formula (R⁴)₂ PCH(R⁵)C(S)R⁶wherein R⁴, R⁵ and R⁶ are defined as above

The amount of catalyst employed in the copolymerization process of thisinvention is not critical and may vary from about 0.001% to about 50%,by weight, based on the combined weights of catalyst, ethylene andcomonomer(s) used. Preferably, the amount of catalyst is about 0.001% toabout 15%, by weight.

Known poisons for the catalysts used in the invention process includeexcessive amounts of oxygen, water, inorganic and organic acids, alkylhalide, strongly binding ligands, such as phosphines or arsines,pyridines, sulfides and aluminum trialkyls (although boron trialkyls arenot poisonous). When catalyst poisons are known to be present, scavengermolecules may be added to "neutralize" them. Thus, for example, whenwater or acids are present, addition of titanium tetraalkoxides, alkylaluminumdi-(2,6-di-t-butyl-4-methyl)phenoxide or[(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane will complex orreact with the poisons to give inert products. Also, the scavengers canbe heterogeneous; for example, molecular sieves which can bind smallmolecules such as water and inorganic or organic acids or bases.

The catalysts themselves may be supported on a heterogeneous support,such as the newly-formed polymer, anion exchange resins, inorganichydroxides or oxides, such as calcium hydroxide or silica, or inorganicsalts, such as nickel(II) chloride, calcium chloride or magnesiumchloride. These supports may immobilize the homogeneous catalysts andthus increase their lifetime.

Ethylene and the comonomer(s) are contacted with a solvent containingthe catalyst, or with only the solvent into which the catalyst is laterinjected at the reaction temperature. The catalyst may also beintermittently or continuously added to the polymerization reactor.Comonomer(s), which may also serve as solvent, may be introduced at anytime during the polymerization, at a concentration of about 0.1 to 50%,by weight, of solvent. The amount of comonomer(s) present duringpolymerization, and the pressure of ethylene employed, determine theamount of comonomer incorporated into the polymer. An increase inethylene pressure may also increase the molecular weight of thecopolymer. Copolymer molecular weight can also be influenced by factorswhich affect catalyst activity, such as solvent polarity and thepresence of ligands, such as triphenylphosphine or amines.

Suitable solvents include non-polar organic solvents, such as linear orbranched alkanes and cycloalkanes, such as pentane, isooctane andcyclohexane, and mixtures thereof, as well as aromatic solvents, such asbenzene, toluene and xylenes. Polar solvents include ethers, such asdiethylether, ethylene glycol dimethyl ether, tetrahydrofuran anddioxane; esters, such as ethyl acetate and methyl benzoate; ketones,such as acetone and methylethylketone; amides, such as formamide anddimethyl acetamide; nitriles, such as acetonitrile and benzonitrile;alcohols, such a methanol, isopropanol, tert-butanol and ethyleneglycol; amines, such as tri-n-butylamine and N-methylpyrrolidine;sulfur-containing solvents, such as dimethylsulfoxide and sulfolane;fluorocarbons; triethyl phosphate; nitromethane; and tetraethylsilicate.

Additives, such as 2,6-di-tert-butyl-4-methylphenol and its reactionproducts with trimethylaluminum, as well as titanium(IV) alkoxides, suchas titanium(IV) isopropoxide, can also be included in the polymerizationreaction mixture. Such additives serve as stabilizers in the finalpolymer or to scavenge excess water or small amounts of acids which aredeleterious to the catalyst.

The polymerization reaction should be carried out in an oxygen-freeatmosphere, such as argon, nitrogen, hydrogen, carbon dioxide or sulfurdioxide.

Copolymerization is carried out in a temperature range of about 0° C. toabout 200° C., preferably about 20° C. to about 120° C. Ethylenepressure may vary from about 1 psig (6.9 kPa) to about 10,000 psig(69,000 kPa), preferably about 10 psig (69 kPa) to about 3,000 psig(20,700 kPa). Copolymerization can be carried out in batch, continuousor semi-continuous facilities. The copolymer can be isolated byconventional techniques, such as filtration, centrifugation, solventevaporation, or by precipitation in a non-solvent, such as methanolOptionally, an acid, such as hydrochloric acid, may be added to theprecipitant to help remove spent catalyst from the polymer.

The unreacted comonomer(s) and spent catalyst can be removed from thecopolymer by extraction into a solvent in which the copolymer isinsoluble Such solvents, which include alcohols, ketones and tertiaryamines, should be selected so that they can be easily separated from thecomonomer(s) by distillation or extraction. Spent catalyst can berecovered by crystallization or extraction with water, which may containsmall amounts of acid.

The copolymers prepared by the process of this invention will usuallyhave molecular weights (M) in the range of about 1000 to over 100,000.The copolymers are useful in a wide variety of commercial applications,as will be known to those skilled in the art, including, for example,molding resins for producing shaped articles, such as films, membranesand molded objects; polymeric plasticizers; polymeric compatibilizersfor normally incompatible polymers, such as polyethylene and nylon;dye-site resins; polymeric binders for glass fibers and minerals;cross-linking agents; ion-exchange materials; adhesives; polymericreinforcing additives for oils; supports for drug delivery; and waxesand other hydrocarbon products.

In the following examples which are embodiments of the invention, partsare by weight and temperatures are in degrees Celsius unless otherwiseindicated. All reactions were conducted in an atmosphere of nitrogen.Immediately following is a description of three different preparationsof catalyst component 3(i), any one of which, when mixed with a suitablealkylating or arylating agent, forms catalyst mixture (3) of theinvention.

To 7.1 g (18.7 mmol) of (benzoylmethylene)-triphenylphosphorane and 2.6g (9.5 mmol) of bis(cyclooctadiene)nickel(0) was added 300 mL of tolueneand 20 g of methyl methacrylate. After stirring the solution for 19 h at25°, the solvent was removed under reduced pressure and the recoveredsolid was recrystallized from a mixture of methylene chloride-ethanol bypartially removing the methylene chloride under reduced pressure to give3.8 g of ##STR10## as deep orange crystals. Further reduction of thesolvent gave an additional 0.8 g for a combined yield of 75%. Thecrystals and its solutions are air-stable.

Using a procedure substantially the same as that described above, exceptthat the phosphorane used was[benzoyl(phenyl)methylene]triphenylphosphorane, a 30% yield of ##STR11##was obtained.

A small pressure bottle was charged with 100 mg 0.15 mmol) of ##STR12##and 10 mL of methanol. After a brief evacuation, the bottle was chargedto 80 psig (552 kPa) with hydrogen sulfide. The pressure was releasedafter 5 minutes and the methanol was evaporated. The solid was dissolvedin a small amount of methylene chloride; the solution was treated withcharcoal and filtered; the charcoal was washed with a small amount ofethanol. On removing part of the solvent 60 mg of honey-colored crystalsof ##STR13## was collected and dried.

EXAMPLE 1 Catalyst Mixture (3) and Catalyst 1(c)

To 1.10 g (1.68 mmol) of ##STR14## and 75% mL of toluene was added 0.18g (2.50 mmol) of trimethylaluminum. After a homogeneous honey-brownsolution was obtained, 5 mL of ether and 20 mL of hexane were added. Onstanding, ##STR15## Catalyst 1(c), precipita as an orange solid whichwas collected and washed with hexane. The yield was 1.1 g (90%).

EXAMPLE 2 Catalyst 1(b)

To 3.20 g (8.42 mmol) of (benzoylmethylene)triphenylphosphorane, 2.31 g(8.42 mmol) of bis(1,5-cyclooctadiene)nickel(0), and 10.8 g of pyridinewas added 200 mL of toluene. The mixture was briefly heated to 50°,allowed to cool to 25°, and stirred for 16 h. After the addition ofdiatomaceous earth filter aid the solution was filtered to remove asmall amount of nickel metal. The solvent was removed under reducedpressure. The yellow solid was collected to give, after a hexane wash,3.8 g of yellow solid ##STR16##

which was purified from warm toluene to which hexane was added.

EXAMPLE 3 CataIyst 1 (b)

The procedure of Example 2 was followed, except that q-picoline wassubstituted for pyridine and the phorphorane Ph₂ P═C(SO₃ Na)C(O)Ph wassubstituted for (benzoylmethylene)triphenylphosphorane. The product was##STR17##

EXAMPLE 4 Catalyst 1(b)

The procedure of Example 2 was followed, except that the phosphorane Ph₂P═C(SO₃ Na)C(O)Ph (4.8 g) was used instead of the(benzoylmethylene)triphenylphosphorane. Yield of ##STR18## was 4.9 g.

EXAMPLE 5 Catalyst 1(b)

The procedure of Example 2 was followed, except that(benzoylmethylene)(diphenyl)methylphosphorane (3.3 g) was substitutedfor (benzoylmethylene)triphenylphosphorane. The product was ##STR19##

EXAMPLE 6 Catalyst Mixture (2) and Catalyst 1(a)

A freshly-prepared 70 mL-benzene solution of 2.70 g (4.87 mmol) ofCatalyst Component 2(i), ##STR20## and 0.68 g (2.64 mmol) of acceptorcompound 2,4-pentanedionatobis(ethylene)rhodium(I), was promptlyfiltered to remove a small amount of insolubles. 0n standing, 0.69 g ofhoney-brown crystals of [PhNi[Ph₂ PCH═C(O)Ph]₂, Catalyst 1(a),precipitated; this was collected and washed with a small amount ofbenzene. After heating the filtrate to 60° and adding 130 mL of benzeneand 50 mL of hexane the solution yielded, after 72 h, an additional 0.25g of crystals, for a combined yield of 44%.

EXAMPLES 7-18

The compounds prepared in these examples are species of catalyst mixturecomponent (2)(i), of formula hereinabove, wherein L² is P(R¹)₃, X¹ is Oand E¹ is P. The compounds of Examples 7-13 and 16-18 were prepared byprocedures similar to those of Keim et al., supra. The compounds ofExamples 14 and 15 were prepared by the procedure described in U.S. Pat.No. 4,293,502. In each case, catalyst mixture (2) of the invention wasprepared by mixing an acceptor compound, as described above, with thecatalyst components prepared in these Examples 7-18. The symbolsrepresented in the aforesaid formula are tabulated in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Ex.                                                                              R.sup.3                                                                              R.sup.4 R.sup.4                                                                          R.sup.5                                                                            R.sup.6                                                                            R.sup.1                                        __________________________________________________________________________     7 Ph     Ph      Ph H    Ph   Ph                                              8 Ph     Ph      Ph Ph   OCH.sub.3                                                                          CH.sub.2 CH.sub.3                               9 Ph     Ph      Ph Ph   Ph   CH.sub.2 CH.sub.3                              10  -p-CF.sub.3 C.sub.6 H.sub.4                                                         Ph      Ph H    Ph   CH.sub.2 CH.sub.3                              11 Ph     Ph      Ph Ph   OCH.sub.3                                                                          Ph                                             12 Ph     Ph      Ph Ph   OCH.sub.3                                                                          CH.sub.3                                       13 Ph     Ph      Ph Ph   Ph   Ph                                             14 Ph     Ph      Ph SO.sub.3 Na                                                                        Ph   Ph                                             15 Ph     Ph      Ph SO.sub.3 Na                                                                        OCH.sub.3                                                                          Ph                                             16 Ph     Ph      Ph H    Ph    -p-CF.sub.3 C.sub.6 H.sub.4                   17 Ph      -o-CH.sub.3 OC.sub.6 H.sub.4                                                         Ph H    Ph   Ph                                             18 Ph      -o-CH.sub.3 OC.sub.6 H.sub.4                                                         *  H    Ph   Ph                                             __________________________________________________________________________     *-oCH.sub.3 OC.sub.6 H.sub.4                                                  Ph = C.sub.6 H.sub.5                                                     

EXAMPLE 19 Catalyst 1(b)

The procedure of Example 2 was followed, except that[benzoyl(phenyl)methylene]triphenylphosphorane (5.05 g) was used insteadof (benzoyl methylene)triphenylphosphorane. The yield of ##STR21## was5.3 g.

UTILITY EXAMPLE 20 Copolymerization of Ethylene and Methyl 4-Pentenoate

A 250 mL pressure bottle was charged with 200 mg of catalyst mixture (2)comprised of equal parts of catalyst component 2(i), prepared as inExample 7, and the acceptor compound2,4-pentanedionatobis(ethylene)rhodium(I), together with 50 mL oftoluene and 5 mL of methyl 4-pentenoate (M4P). After attaching apressure head, the bottle was evacuated and charged to 50 psig (345 kPa)with ethylene. The bottle was partially immersed in a 50° oil bath,stirred magnetically, and repressured periodically to 50 psig (345 kPa)with ethylene. After 135 minutes the pressure was reduced and solventand unreacted comonomer were removed under reduced pressure to give,after washing with methanol, 1.4 g of a white ethylene copolymercontaining 3.6% of M4P.

EXAMPLE 21 Copolymerization of Ethylene and M4P

A 100 mL toluene solution containing catalyst mixture (4) comprised of1.0 g of bis(1,5-cyclooctadiene)nickel(0) and 1.54 g of (C₆ H₅)₃ P═C(CO₂CH₃ was stirred for 24 h at 25°. The solution was filtered to give aclear red-brown solution. A pressure bottle was charged with 50 mL ofthis solution and 2 g of M4P. After briefly evacuating, the bottle wascharged to 50 psig (345 kPa) with ethylene and placed in a 50° oil bathfor 75 minutes. The ethylene was released and solvent and excesscomonomer were removed under reduced pressure to give, after a hexaneand methanol wash, 3.1 g of a gray polymer. This polymer (2.6 g), 100 mLmethanol, and 2 mL of conc. hydrochloric acid were refluxed for 30minutes. The now white polymer was collected on a filter, washed withmethanol, and dried at 25°/0.01 mm Hg for 27 h. The infrared spectrumshowed strong ester absorption at 1742 cm⁻¹. The polymer softened at80°-85° and melted at 150°; molecular weight, MHD w, 11,000; dispersity2.87. Analysis showed it to be an ethylene copolymer containing 6.5% ofM4P.

EXAMPLE 22

A procedure similar to that of Example 21 was used, except that 5 mL of5-hexene-2-one (5H20) was substituted for the 2 g of M4P. After 195minutes 2.0 g of polymer was precipitated with methanol. This polymerwas redissolved in chlorobenzene, treated with activated charcoal,precipitated with methanol and dried. The infrared spectrum showed astrong carbonyl absorption at 1618 cm⁻¹. This ethylene copolymercontained 8.3% of 5H20 and had a of 7,200, with a dispersity of 4.41.

EXAMPLEs 23-39

The following ethylene copolymerization procedure was used in Examples23-39. A 500 mL pressure bottle was charged under nitrogen withcatalyst, cocatalyst, additive(s), comonomer, and solvent as shown inTable 2 (toluene was used as the solvent). A Lab-Crest Scientificmulti-ported head and stirrer assembly outfitted with a thermocouple formeasuring the reaction temperature, a pressure relief valve, aninjection port similar to those found on gas chromatographs, and twovalves (one of which was used as a manual vent; the other was connectedto an ethylene line which contained an in-line pressure regulator andgauge) were attached. The bottle was pressurized to 60 psig (414 kPa)with ethylene and the contents was stirred at 500 to 1500 rpm. Theethylene valve was closed after 2 minutes and the bottle was partiallyimmersed in a constant-temperature oil bath. The pressure rose initiallydue to the increase in temperature but fell with the onset ofpolymerization and was then kept constant at a 60 psig (414 kPa)ethylene pressure. At times the reaction temperature exceeded the bathtemperature and when this happened, it was usually controlled with anexternal cooling bath. The reaction was terminated by releasing thepressure. The contents of the bottle was then transferred to a 1000 mLbeaker with about 600 mL of methanol. A small amount of 10 Nhydrochloric acid was added and the mixture was stirred until theethylene copolymer was white. It was collected on a filter, washed withseveral portions of methanol to remove unreacted monomers, and dried at25° under reduced pressure. The yields, reaction conditions, and otherpertinent data are given in Table 2. The infrared spectra of theisolated polymers showed comonomer incorporation in all cases.

Regarding Example 29, if the ethylvinyl ether were replaced byvinyltriethoxysilane, the polymerization product would be a copolymer ofethylene and vinyltriethoxysilane.

                                      TABLE 2                                     __________________________________________________________________________                                          Temperature                                      Catalyst                  Sol-  Max Cool-                                                                             React.                                                                            % Comon-                    Cat-                                                                             Wt.                                                                              or                 g      vent                                                                             Oil                                                                              Reac-                                                                             ing Time                                                                              omer                                                                                Yield              Ex.                                                                              alyst                                                                            mg Component                                                                              Comonomer (mL)                                                                             Notes                                                                             (mL)                                                                             Bath                                                                             tion                                                                              Bath                                                                              Min.                                                                              Copolymer                                                                           g                  __________________________________________________________________________    23 4(i) 4(ii)                                                                       200 400                                                                          A B                                                                              ##STR22##                                                                           Si(OC.sub.2 H.sub.5).sub.3                                                              5      70 80 88  No  90  13    10.0               24 2(i) 2(ii)                                                                       300 150                                                                          C A                                                                              ##STR23##                                                                           Si(OC.sub.2 H.sub.5).sub.3                                                              10.7                                                                             1   250                                                                              60 61  Yes 66  --    40.0               25 4(i) 4(ii)                                                                       150 400                                                                          A B                                                                              ##STR24##                                                                           Si(CCH.sub.3).sub.3                                                                     (6)                                                                              2   60 80 81  No  30  --    3.4                26 4(i) 4(ii)                                                                       200 400                                                                          A B                                                                              ##STR25##                                                                           C.sub.4 F.sub.9                                                                         5      60 80 117 No  48  17.6  19.3               27 4(i) 4(ii)                                                                       200 646                                                                          A B                                                                              ##STR26##                                                                           C(CF.sub.3).sub.3                                                                       14 3   60 104                                                                              106 No  30  --    11.5               28 4(i) 4(ii)                                                                       200 400                                                                          A B                                                                              ##STR27##                                                                           OSi(OC.sub.2 H.sub.5).sub.3                                                              0.5 (3)                                                                         3   60 104                                                                              100 No  24  --    9.5                29 2(i) 2(ii)                                                                       100  50                                                                          D E                                                                                     ##STR28##                                                                              5      100                                                                              65 65  No  30   1.4  1.8                30 4(i) 4(ii)                                                                       200 400                                                                          A B                                                                              ##STR29##                                                                           P(O)(OC.sub.2 H.sub.5).sub.2                                                            5  3   60 80 112 No  38  --    12.5               31 4(i) 4(ii)                                                                       150 400                                                                          A B                                                                              ##STR30##                                                                           CN        (2.8)                                                                            4   60 104                                                                              93  Yes 48  --    4.7                32 1(b)                                                                             510                                                                              F                                                                                ##STR31##                                                                           (CH.sub.2).sub.8CO.sub.2 CH.sub.3                                                       13.0   250                                                                              90 94  Yes 120 15.6  45.0               33 2(i) 2(ii)                                                                       200  50                                                                          C A                                                                              ##STR32##                                                                           (CH.sub.2).sub.8CO.sub.2 CH.sub.3                                                       10.0                                                                             5   100                                                                              25 97  No  26  --    14.1               34 4(i)                                                                             150                                                                              A                                                                                ##STR33##                                                                           (CH.sub.2).sub.8 C (O)N(CH.sub.3) CH.sub.2 CH.sub.2N(CH.                      sub.3).sub.2                                                                             5.0   60 80 103 No  69  12.5  20.5               35 2(i) 2(ii)                                                                       200 100                                                                          G E                                                                              ##STR34##                                                                           (CH.sub.2).sub.9 OH                                                                     15.0   70 80 75  No  50  --    3.4                36 2(i) 2(ii)                                                                       200 100                                                                          G A                                                                              ##STR35##                                                                           (CH.sub.2).sub.9 OH                                                                     11.4   100                                                                              80 96  No  32  40    4.8                37 2(i)                                                                             200                                                                              C        1-octene  (40)   60 25 61  Yes 64  --    30                    2(ii)                                                                            100                                                                              A                                                                    38 4(i)                                                                             150                                                                              A        1,5-Hexadiene                                                                           (9)                                                                              6   60 105                                                                              91  Yes 67  --    17.5                  4(ii)                                                                            400                                                                              B                                                                    39 4(i)                                                                             150                                                                              A        1,9-decadiene                                                                           10 7   50 105                                                                              126 No  34  --    18                 __________________________________________________________________________     Catalyst or Component                                                         A. Bis(1,5cyclooctadiene)nickel(0)                                            B. (C.sub.6 H.sub.5).sub.3 PC(C.sub.6 H.sub.5)C(O)C.sub.6 H.sub.5             C. Example 17                                                                 D. Example 11                                                                 E. 2,4Pentanedionatobis(ethylene)rhodium(I)                                   F. C.sub.6 H.sub.5 Ni[(C.sub.6 H.sub.5).sub.2 PC(C.sub.6                      H.sub.5)C(O)C.sub.6 H.sub.5 ]NC.sub.5 H.sub.5                                 G. Example 16                                                                 Notes                                                                         1. Initially, 3 g of comonomer was charged. After 7.5 min, 2.6 g of           comonomer was injected. A similar size charge was injected at 8.5 and 9.5     min into the run, that is, 1 min and 2 min after the first injection.         2. The comonomer was injected after 9.5 min.                                  3. The polymer was precipitated and washed with ethanol.                      4. The comonomer was injected as follows: 0.8 mL at 8.5 min and 2.0 mL at     9.25 min.                                                                     5. Comonomer was mixed with 1.06 of titanium isopropoxide to remove trace     of acid.                                                                      6. Comonomer was injected at 8, 17, and 24 min.                               7. After 10.25 min, a gel formed.                                        

EXAMPLE 40

A 500 mL pressure bottle was charged with 10.6 g of the trimethylsilylester of undecylenic acid and 1.06 g of[(1,2-dimethyl-1-propenyl)oxy]trimethylsilane. After 15 minutes 200 mLof toluene and 250 mg of catalyst mixture (2), prepared as in Example22, were added. The pressure head described in Examples 25-41 wasattached, the solution was saturated with 60 psig (414 kPa) ethylene at27° with stirring at 500 rpm. The bottle was partially immersed in an80° oil bath. After 52 minutes very little polymerization had occurred;an additional 250 mg of catalyst was added and the bottle wasrepressured with 60 psig (414 kPa) of ethylene and reimmersed in the 80°oil bath. After 40 minutes the reaction temperature reached 92°; thebath was removed and replaced with an ambient water bath when thereaction temperature reached 101°. The run was terminated after 2 h,after the reaction temperature dropped to 85°. The ethylene copolymerwas precipitated with 300 mL of hexane under nitrogen, allowed to cool,collected on a filter, washed with hexane, and then dried under reducedpressure at 25° for 9 h to give 27.5 g of the ethylene copolymer whichshowed --CO₂ Si(CH₃)₃ absorptions in the infrared spectrum, indicatingthe presence of the undecylenate comonomer.

EXAMPLE 41

A 500 mL pressure bottle was charged with 9.5 g of the macromonomer CH₂═CHCH₂ C(C₆ H₅)₂ [CH₂ C(CH₃)CO₂ CH₃ ]_(2O) H, (MHD w═2370, with adispersity of 1.02), 100 mL of tetrahydrofuran and catalyst mixture (4)comprised of 400 mg of (C₆ H₅)₃ P═C(C₆ H₅)₂ C(O)C₆ H₅ and 200 mg ofbis(1,5-cyclooctadiene)nickel(0). The

pressure head described for Examples 24-40 was attached and the solutionwas saturated with 60 psig (414 kPa) of ethylene for 2 minutes at 24°with stirring at 500 rpm. The bottle was partially immersed in a 106°oil bath. Within 5 minutes the reaction temperature rose to 64° and thepressure to 81.5 psig (562 kPa), and after 8 minutes the temperature was89° and the pressure was 60 psig (414 kPa). At this point, the valve toa constant 60 psig (414 kPa) ethylene supply was opened and thepolymerization was continued with the bottle removed from the oil bath.With only ambient air cooling, the reaction temperature reached 97°after 15 minutes. After 54 minutes the reaction temperature dropped to46° and the run was terminated by releasing the pressure and pouring thepolymer solution into 500 mL of methanol. The polymer was collected,redissolved in 150 mL of hot toluene containing 2 mL of 10 Nhydrochloric acid, reprecipitated with 500 mL of methanol, washed withmethanol and extracted with ethyl acetate and methylene chloride, inwhich the macromonomer is soluble, and dried to give 16.0 g of theethylene copolymer containing 24.8% of the macromonomer. The averagemolecular weight, MHD 2, was found to be 13,900, with a dispersity of1.93.

EXAMPLE 42

A 500 mL pressure bottle was charged with 100 mg of the catalystcomponent prepared as in Example 8, 100 mg of the acceptor compound2,4-pentanedionatobis(ethylene)rhodium(I), 100 mL of toluene and 5.0 gof styrene. A procedure similar to that of Example 20 was followed togive, after 260 minutes, 25.5 g of ethylene copolymer which by infraredanalysis showed styrene incorporation. Solvent-extraction of the polymerwith methylene chloride, acetone or tetrafluorofuran yielded a waxymaterial which, except for slight IR intensity changes, was identical tothe unextracted polymer. Differential scanning calorimetric analysisshowed a sharp endotherm at 118° with a broad shoulder at 50°-110°.

EXAMPLE 43

A 500 mL pressure bottle was charged with catalyst mixture (4) comprisedof 400 mg of [benzoyl(phenyl)methylene]triphenylphosphorane and 200 mgof bis(1,5-cyclooctadiene)nickel(0), together with 60 mL of toluene, 10g of styrene, and 5 g of 4-triethoxysilyl-1-butene. A procedure similarto that used in Examples 23-39 was followed. Using an 80° oil bath, thereaction temperature reached 97°. After 78 minutes, the ethylenecopolymer was precipitated in a dry nitrogen atmosphere with 10 mL ofhexane and 600 mL of ether and collected. After drying at 0.005 mm Hg,22° and 18 h, 15.0 g of light grey copolymer was obtained. Its infraredspectrum showed the presence of both comonomers in the polymer.

EXAMPLE 44

A 500 mL pressure bottle was charged with 2.8 g of (OC)₅ CrP(C₆ H₅)₂(CH₂)₃ CH═CH₂, 200 mg of catalyst component 2(i), prepared as in Example14, 100 mg of bis(1,5-cyclooctadiene)nickel(0), and 100 mL of toluene.The procedure used in Examples 25-41 was followed using a 92° oil bath.The reaction temperature reached 83° after 113 minutes, when the run wasterminated. The ethylene copolymer was precipitated with methanol,redissolved in toluene, precipitated with methanol and extracted withboiling methylene chloride to give 1.5 g of a light yellow copolymer.The infrared spectrum showed three carbonyl absorptions at 2065(m),1985(w) and 1936(vs) cm⁻¹, of the pentacarbonylchromium moiety, besidesthe CH vibrations for the polyethylene backbone.

EXAMPLE 45

An ethylene copolymer containing 13 wt % of the methyl ester ofundecylenic acid, with an average molecular weight of 5,820 and adispersity of 2.3 (similar to Examples 32 and 33), was fractionated at60° by size-exclusion chromatography using uninhibited toluene as thesolvent. Various fractions, each representing a narrow distribution ofpolymer molecular weights, were collected. Each fraction was mixed withdry potassium bromide, solvent was removed under reduced pressure, andthe mixture was analyzed by FT-IR spectroscopy. Each fraction absorbedat 1745 cm⁻¹, due to the ester moiety, showing unequivocally that themethyl ester of undecylenic acid was incorporated into all polymermolecular weight fractions.

BEST MODE FOR CARRYING OUT THE INVENTION

The best mode presently contemplated for carrying out the invention isdemonstrated by all of the Examples.

What is claimed is:
 1. The catalyst precursor mixture comprising:(i) thenickel compound of the formula ##STR36## wherein: R³ and each R⁴,independently, is H or C₁₋₂₀ hydroalkyl; X¹ is O or S; E¹ is P, As orSb; and each of R⁵ and R⁶, independently, is H, C₁₋₂₀ hydrocarbyl or afunctional group selected from --OR² --Cl, --CO₂ R², --CO₂ M,--C(O)N(R¹)₂, --C(O)R², --SR², --SO₂ R², OSO₂ R², --SOR²,--P(O)(OR²)_(2-y) (R¹)_(y), --CN, --NHR², --N(R²)₂, ##STR37##--Si(OR¹)_(3-x) (R¹)_(x), --OSi(OR¹)_(3-x) (R¹)_(x), --NO₂, --SO₃ M,--PO₃ M₂ and --P(O)(OR²)₂ M wherein M is alkali or alkaline earth metal,ammonium, quaternary ammonium, phosphonium or arsonium, y is 0, 1 or 2,each R¹ independently, is H or C₁₋₂₀ hydrocarbyl and x is 0 or aninterger of 1 to 3 or R⁵ and R⁶, taken together, is a substituted orunsubstituted C₅₋₈ alicyclic, C₅₋₈ heterocyclic or C₆₋₁₄ aromatic ring,the heteroatom of the heterocyclic ring being selected from O, N and S;asnd L² is a strongkly coordinating ligand; and (ii) an acceptorcompound
 2. The catalyst precursor mixture comprising(i) the nickelcompound of the formula ##STR38## wherein: R⁴ is H or C₁₋₂₀ hydrocarbyl;X¹ is O or S; E¹ is P, As or Sb; and each of R⁵ and R⁶, independentl, isH, C₁₋₂₀ hydrocarbyl or a functional group selected from --OR², Cl,--Co₂ R², --CO₂ M, --C(O)N(R¹)₂, --C(O)R², --SR², --SO₂ R², --OSO₂ R²,--P(O)(OR²)_(2-y) (R¹)_(y), --CN, --NHR², --N(R²)₂, ##STR39##--Si(OR¹)_(3-x) (R¹)₂, --OSi(OR¹)_(3-x) (R¹)₂, --NO₂, --SO₃ M, --PO₃ M₂and --P(O)(OR² ₂ M wherein M is alkali or alkaline earth metal,ammonium, quaternary ammonium, phosphonium or arsonium, y is 0, 1 or 2and R¹, each R², independently, and x are as defined above, or R⁵ andR⁶, taken together, is a substituted or unsubstituted C₅₋₈ alicyclic,C₅₋₈ heterocyclic or C₆₋₁₄ aromatic ring, the heteroatom of theheterocyclic ring being selected from O, N or S; (ii) an alkylating orarylating compound.
 3. Catalyst precursor mixture of claim 1 wherein R³is methyl, phenyl or p-trifluoromethylphenyl, each R⁴ is methyl, phenylor o-methoxyphenyl, R⁵ is H, methyl phenyl or --SO₃ Na, R⁶ is methyl,phenyl or methoxyl, X¹ is O, E¹ is P, and L² is P(R¹)₃ wherein R¹ ismethyl, ethyl, phenyl or p-trifluoromethylphenyl.
 4. Catalyst mixture ofclaim 2 wherein each of R⁴ or R⁵ is methyl or phenyl asnd R⁶ is H,methyl or phenyl.